EP0206133A1 - Use of polypyrrole to deposit metallic copper onto non-electroconductive materials - Google Patents

Use of polypyrrole to deposit metallic copper onto non-electroconductive materials Download PDF

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Publication number
EP0206133A1
EP0206133A1 EP86107994A EP86107994A EP0206133A1 EP 0206133 A1 EP0206133 A1 EP 0206133A1 EP 86107994 A EP86107994 A EP 86107994A EP 86107994 A EP86107994 A EP 86107994A EP 0206133 A1 EP0206133 A1 EP 0206133A1
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EP
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Prior art keywords
monomers
materials
solution
oxidizing agent
polypyrrole
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EP86107994A
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German (de)
French (fr)
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EP0206133B1 (en
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Herbert Dr. Naarmann
Walter Dr. Heckmann
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BASF SE
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BASF SE
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Priority claimed from DE19853520980 external-priority patent/DE3520980A1/en
Priority claimed from DE19853535709 external-priority patent/DE3535709A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating

Definitions

  • the invention relates to a method for applying layers of etekirisch conductive polymers to other materials.
  • the object of the invention was to apply readily adhesive layers of electrically conductive polymers to other materials in a technically simple manner.
  • This object is achieved by a process which is characterized in that monomers from the class of 5-membered or 6-membered heterocycles which contain nitrogen or sulfur as heteroatoms are applied to the surface of the material and the monomers are polymerized with an oxidizing agent .
  • the method of the invention can in principle be applied to all solid materials.
  • the shape of the materials can be of any type, for example the materials can have dimensions in one direction that are a multiple of the dimensions transverse to it.
  • the materials can e.g. in the form of rods, tapes, wires or fibers.
  • the materials can also have a two-dimensional dimension that is a multiple of the thickness of the material. So you can e.g. Apply layers of conductive polymers to plates, sheets, foils or films of the materials. It is also possible to apply the layers to materials of any shape, e.g. such as they have technical components, machine elements or switching elements.
  • Non-conductors are suitable as materials, but also electrical conductors such as metals.
  • Non-conductive are e.g. thermoplastics, such as polyols. fine, polystyrene, polyamides, polyethers, polyurethanes, polyether sulfones, polyimides or polyamideimides. Polytetrafluoroethylene, polyesters, polyether ketones, polysulfones and polyetherimides can also be coated by the process according to the invention.
  • Inorganic materials such as e.g. Glass or other silicate materials in question.
  • Other suitable inorganic materials are e.g. Clay, ceramic materials, titanium dioxide (rutile, anatase), titanates and single crystals of Seignette salt.
  • the above-mentioned titanates and single crystals of Seignette salt have a pronounced anisotropy of certain properties.
  • the coating with electrically conductive polymers makes it possible to e.g. to be used in electrical switches.
  • the surface of these materials can be smooth or open-pored and both crystalline and amorphous materials can be used.
  • metallically conductive materials steel, titanium, cobalt, chromium, vanadium, aluminum, copper or any alloys of these materials are also suitable.
  • metals in the method according to the invention it becomes possible to adapt the electrical resistance of the metal surface according to the conductivity of the electrically conductive polymers, which is advantageous in some cases (e.g. shielding of high-frequency waves).
  • the method according to the invention is also suitable for coating glued or unglued wood-based materials, e.g. Chipboard, sawdust and wood itself.
  • the monomers used according to the invention are selected from the class of 5-membered and 6-membered heterocycles which contain nitrogen or sulfur as heteroatoms. Preferably, these compounds also contain a conjugated ir electron system.
  • Examples of these compounds are those from the class of pyrroles and thiophenes.
  • pyrroles e.g. the unsubstituted pyrrole itself but also N-substituted pyrroles, such as N-alkylpyrroles.
  • substituted pyrroles such as 3,4-dialkylpyrroles with C, -C, alkyl groups or 3,4-dichloropyrroles, can also be used.
  • unsubstituted thiophene itself and 2-or 3-alkylthiophenes e.g. 2,3-diethylthiophene.
  • 5-membered heterocyclic compounds mentioned can also be used together with other copolymerizable compounds, e.g. Furans, thiazole, oxazole or imidazole can be polymerized. From the class of 6-membered heterocycles only aniline or benzidine are mentioned here.
  • the oxidizing agent used is advantageously an oxygen-containing oxidizing agent which, based on 1 mole of the compound to be polymerized, can be used in amounts of 0.1 to 2 moles. Larger amounts of oxidizing agent are not necessary since the amount is sufficient to convert the entire monomers into polymers.
  • peroxo acids and their salts such as peroxodisulfuric acid and their alkali and ammonium salts
  • peroxoborates, perchlorates or peroxochromates such as sodium perborate, potassium dichromate or iron perchlorate and copper perchlorate are also preferably used.
  • Permanganates such as potassium permanganate are also suitable if small amounts of acid are added to them.
  • Hydrogen peroxide can also be used, the presence of conductive salts generally being very advantageous here.
  • PbO 2 or oxidizing agents based on Mn - (III) can also be used.
  • the oxidizing agents can possibly be applied to the surface of the material together with a conducting salt or the monomers together with a conducting salt.
  • the polymerization of the monomers can therefore take place in the presence of conductive salts, which are also referred to as complexing agents or doping agents.
  • conductive salts include KHSO., Na 2 SO 4 , HCOOH, LiClO 4 , HCIO., Net 4 ClO 4 , NBu ⁇ , CIO ,, KAIF J , NaAIF 6 , KBF ,, K 2 ZrF 6 , K 2 NiF 4 , HO 2 (NO 3 ) 2 , H 2 SO 4 , FeCl 3 , NOPF., KAsF. or NaPF. proven.
  • the concentration of the conductive salts is advantageously such that at least 1 mol of the conductive salts listed above are used per 3 mol of the monomers used or of the mixtures of the monomers; if, for example, FeCl 3 or FeClO 4 is used, such compounds act equally as conductive salts and as oxidizing agents.
  • Sulphonic acids of pyrrole or thiophene can be used both as monomers and as conducting salts.
  • an oxidizing agent is first applied to the surface of the material.
  • This is expediently carried out in solution, water having proven useful as a solvent, if appropriate in a mixture with organic, water-miscible solvents.
  • organic solvents such as dimethyl sulfoxide, methanol, acetonitrile, ethylene carbonate, propylene carbonate, dioxane or tetrahydrofuran can also be used.
  • the solutions contain 0.1 to 50% by weight, preferably 1 to 20% by weight, of the oxidizing agent.
  • the amount of the oxidizing agent to be added is advantageously from 0.1 to 2 mol per mol of the compound to be polymerized.
  • the monomers can be applied from the gas phase or from a solution. Both options are explained in more detail later.
  • a solution of the monomer is first mixed with a solution of the oxidizing agent.
  • the solvents mentioned in the above process variant are suitable as solvents.
  • the reaction partners can be distributed in an ultrasound field.
  • detergents can also be added, preferably in an amount of 0.01 to 10% by weight, based on the monomers used.
  • a solution of the monomer and a solution of the oxidizing agent, optionally with the conductive salt are mixed and immediately afterwards the mixture is applied to the surface of the material.
  • the mixing of the solution is expediently carried out in a mixing device suitable for such purposes, such as mixing devices for two-component paints or mixing devices which serve as two-component spraying devices.
  • the solutions are advantageously mixed in finely divided form and the mixture is applied to the surface of the materials.
  • the mixture should be distributed on the surface of the material.
  • the two-component spray devices to be used advantageously for such working methods are known and are used in various variants in technology.
  • An advantage of this embodiment is that it enables the continuous coating of materials with electrically conductive polymers in a technically very simple manner by continuously applying the materials to be coated to the spraying or. Spray device passes.
  • This variant is particularly suitable for the continuous coating of polymer films with antistatic coatings.
  • the monomer to be applied is mixed in a solvent or in dispersion (solution I) and a solution of the oxidizing agent, preferably together with an acid (solution II) in a mixing device and continuously applied to the spray or.
  • the monomers can be in a solvent such as e.g. Ethanol or mixtures of alcohols with water, but also in polymer solutions, e.g. a solution of polyphenyl sulfone in dichloromethane.
  • concentration of the monomers which provide the electrically conductive polymer is advantageously 1 to 25% by weight.
  • the concentration of oxidizing agent and, if appropriate, the acid in the solution which is mixed with the monomer solution is generally likewise not more than 25% by weight - (oxidizing agent and acid in each case).
  • organic sulfonic acids e.g., as acids which can be added to the oxidizing agent solution.
  • Anthraquinone sulfonic acid and phenyl sulfonic acid and their derivatives have been proven.
  • a further process variant consists in first applying the monomers to the surface of the materials and then the oxidizing agent.
  • the material to be coated can be in a solvent, e.g. in ethanol, acetone or water, and be soaked with the monomers. The monomer is then converted into polymers by adding the oxidatron.
  • a solvent e.g. in ethanol, acetone or water
  • the material may optionally be subjected to a treatment, e.g. with acid, to increase the adhesion of the monomers to the material.
  • a treatment e.g. with acid
  • the application from the gas phase is advantageously carried out by transferring the materials to be coated (treated or untreated; before or after applying the oxidizing agent and / or conductive salt) into a vessel, evacuating the vessel and then treating the material with monomer vapors.
  • the monomers from the gas phase it is advantageous to completely remove any solvents that may still be present in the treatment of the material.
  • aqueous and alcoholic solvents, ethers, tetrahydrofuran and acetone have proven themselves as solvents for the variant of applying the monomers from a solution, to name just a few.
  • the thickness of the layers of electrically conductive polymers applied to the materials is variable within wide limits, but is generally in the range from 0.1 to 100 ⁇ m. For special applications, however, the layers can be either thicker or thinner.
  • the monomers are polymerized in a temperature range from 0 to 500.degree. C., preferably between 20 and 250.degree.
  • the pressure at which the polymerization is carried out is not critical per se. It is expedient to work at a pressure in the range from 10 kPa to 100 MPa.
  • the electrical conductivity of the applied polymers is generally in the range from 10 7 to 10 + Scm- ', in particular in the range from 1 0 3 to 10 Scm-'.
  • the layer of the conductive polymer can only be applied to certain points on the material, ie patterns, pictures or characters or switching arrangements can be applied to the material. It is also possible to provide the entire material with a conductive polymer layer after the process. It is sometimes appropriate to repeat this process several times, whereby different conductive polymers can be stacked on top of each other. As already mentioned, the layer of the conductive polymer adheres firmly to the layer of the material. An improvement in the adhesive strength of the electrically conductive layer on the materials is achieved in many cases by tempering at 80 to 150 ° C. (of course depending on the softening temperature of the material to be coated).
  • the process according to the invention can be used, for example, to produce antistatic films or films for packaging which are used for packaging substances which have to be electrically shielded.
  • Pressure switches and circuits for fixing information can also be produced by the method of the invention.
  • Composites made by the process can be used for photovoltaic elements.
  • the materials obtained by the process according to the invention are also suitable as conductor tracks and as electrode material.
  • conductor tracks When used as conductor tracks, a subsequent modification by laser or other high-energy radiation can take place.
  • the deposition of metallic copper may be mentioned as an example of the use as an electrode material.
  • Inorganic materials which have been coated by the process according to the invention are suitable, for example as dielectrics, for the production of electrodes and for shielding electromagnetic waves, and as sensors.
  • the surface of a polyester film (42 .mu.m thick) was coated with a 10% by weight ethanolic solution of iron perchlorate. The solvent was allowed to evaporate and the film thus treated was exposed to a nitrogen atmosphere containing 10% by volume of pyrrole vapor at a temperature of 150 ° C. for 30 seconds. Within a few seconds a black layer formed on the film surface.
  • This insoluble polypyrrole coating had a specific conductivity of 10- 'S / cm.
  • Example 2 The procedure was as in Example 1, but polyethersulfone was used as the film material.
  • the specific conductivity of the formed polypyrrole film was 10- 'S / cm.
  • a film of polyamide 30 ⁇ m thick was coated with an aqueous solution containing 10% by weight sodium peroxydisulfate and 5% by weight benzenesulfonic acid. The water was evaporated and the film thus treated was exposed to an atmosphere consisting of nitrogen and pyrrole vapor as described in Example 1. An insoluble, adherent film was formed which had a specific conductivity of 0.2.10- 'S / cm.
  • Example 2 The procedure was as described in Example 1, but a solution containing 10% by weight of iron perchlorate and 10% by weight of polyvinyl alcohol was applied and the water was evaporated off. After exposure to the pyrrole atmosphere, a polypyrrole film was obtained which adhered firmly to the polyester base.
  • the specific conductivity was 0,6,10- 2 S / cm.
  • solution 1 A solution of 10% by weight pyrrole in ethanol (solution 1) and an aqueous solution of 10% by weight Na 2 S 2 O 8 (sodium peroxydisulfate) (solution II) were mixed in a two-component spray gun and rinsed vertically against a polished piece of wood. The workpiece was rinsed with solution I + II for 10 seconds and then dried at 60 ° C. (1 hour at 10 torr). The result was a firmly adhering layer of a black, electrically conductive polymer with a conductivity of 8 S / cm.
  • the solutions and II (as in Example 1) were mixed and the piece of wood was stored in the solution for 20 seconds.
  • the conductivity of the electrically conductive coating was 5 S / cm after drying.
  • Solutions I and 'II (as in Example 2) were mixed and a tissue (linen, 10 x 10 cm) was stored in the solution for 20 seconds.
  • the conductivity after drying was 2.8 S / cm.
  • Example 2 The procedure was as in Example 1, but solution 1 additionally contained 3% by weight of benzenesulfonic acid. Following the procedure as in Example 1, an electrically conductive layer with a conductivity of 7 S / cm was obtained.

Abstract

A process in which monomers from the group comprising the 5- and 6- membered heterocyclics containing nitrogen or sulphur as heteroatom are applied to the material and polymerised with an oxidising agent.

Description

Die Erfindung betrifft ein Verfahren zum Aufbringen von Schichten aus etekirisch leitfähigen Polymeren auf andere Materialien.The invention relates to a method for applying layers of etekirisch conductive polymers to other materials.

Nach einer Arbeit von K.C. Khulke und R.S. Mann, Journal of Polymer Science, Vol. 20 (1982), Seiten 1089 bis 1095 kann Pyrrol in wäßriger Lösung unter der Einwirkung von Oxidationsmitteln polymerisiert werden, so daß sich das Polymerisat in Form eines feinteiligen schwarzen Pulvers abscheidet. Diese Polymerisate eignen sich jedoch nur schlecht zur Beschichtung von anderen Materialien.After a work by K.C. Khulke and R.S. Mann, Journal of Polymer Science, Vol. 20 (1982), pages 1089 to 1095, pyrrole can be polymerized in aqueous solution under the action of oxidizing agents, so that the polymer separates out in the form of a finely divided black powder. However, these polymers are poorly suited for coating other materials.

Aufgabe der Erfindung war es, gut haftfähige Schichten aus elektrisch leitfähigen Polymeren auf technisch einfache Weise auf andere Materialien aufzubringen.The object of the invention was to apply readily adhesive layers of electrically conductive polymers to other materials in a technically simple manner.

Diese Aufgabe wird durch ein Verfahren gelöst, welches dadurch gekennzeichnet ist, daß man auf die Oberfläche des Materials Monomere aus der Klasse der 5-gliedrigen oder 6-gliedrigen Heterocyclen, die Stickstoff oder Schwefel als Heteroatome enthalten, aufbringt und die Monomeren mit einem Oxidationsmittel polymerisiert.This object is achieved by a process which is characterized in that monomers from the class of 5-membered or 6-membered heterocycles which contain nitrogen or sulfur as heteroatoms are applied to the surface of the material and the monomers are polymerized with an oxidizing agent .

Bevorzugte Ausführungsformen des erfindungsgemäßen Verfahrens sind den Unteransprüchen zu entnehmen.Preferred embodiments of the method according to the invention can be found in the subclaims.

Es hat sich gezeigt, daß nach dem erfindungsgemäßen Verfahren Verbundstoffe aus den Materialien und den elektrisch leitfähigen Polymeren erhalten werden, die in einfacher Weise herstellbar sind und festhaftende Filme bilden.It has been shown that the process according to the invention gives composites of the materials and the electrically conductive polymers which can be prepared in a simple manner and form firmly adhering films.

Das Verfahren der Erfindung kann auf prinzipiell alle festen Materialien angewendet werden. Die Form der Materialien kann beliebig sein, so können die Materialien beispielsweise Dimensionen in einer Richtung haben, die ein vielfaches der Dimensionen quer dazu betragen. Die Materialien können z.B. in Form von Stäben, Bändern, Drähten oder Fasern vorliegen. Auch können die Materialien eine zweidimensionale Ausdehnung haben, die ein vielfaches der Dicke des Materials beträgt. So kann man z.B. auf Platten, Bahnen, Folien oder Filmen der Materialien Schichten aus leitfähigen Polymeren aufbringen. Ebenso ist es möglich, die Schichten auf Materialien beliebiger Form, z.B. solcher wie sie technische Bauteile, Maschinenelemente oder Schaltelemente haben, aufzubringen.The method of the invention can in principle be applied to all solid materials. The shape of the materials can be of any type, for example the materials can have dimensions in one direction that are a multiple of the dimensions transverse to it. The materials can e.g. in the form of rods, tapes, wires or fibers. The materials can also have a two-dimensional dimension that is a multiple of the thickness of the material. So you can e.g. Apply layers of conductive polymers to plates, sheets, foils or films of the materials. It is also possible to apply the layers to materials of any shape, e.g. such as they have technical components, machine elements or switching elements.

Als Materialien eignen sich Nichtleiter, aber auch elektrische Leiter wie Metalle. Nichtleitend sind z.B. thermoplastische Kunststoffe, wie Polyole- . fine, Polystyrol, Polyamide, Polyether, Polyurethane, Polyethersulfone, Polyimide oder Polyamidimide. Auch Polytetrafluorethylen, Polyester, Polyetherketone, Polysulfone und Polyetherimide können nach dem erfindungsgemäßen Verfahren beschichtet werden. Als nicht-leitende Materialien kommen auch anorganische Materialien, wie z.B. Glas oder andere Silikatmaterialien in Frage. Weitere geeignete anorganische Materialien sind z.B. Ton, keramische Materialien, Titandioxid (Rutil, Anatas), Titanate und Einkristalle von Seignette-Salz. Die vorstehend erwähnten Titanate und Einkristalle von Seignette-Salz weisen eine ausgeprägte Anisotropie bestimmter Eigenschaften auf. Die Beschichtung mit elektrisch leitfähigen Polymeren macht es möglich, dieses Phänomen z.B. in elektrischen Schaltern auszunutzen. Die Oberffäche dieser Materalien kann glatt oder offenporig sein und es können sowohl kristalline als auch amorphe Materialien eingesetzt werden. Von den metallisch leitenden Materialien eignen sich solche auch Stahl, Titan, Kobalt, Chrom, Vanadin, Aluminium, Kupfer oder beliebigen Legierungen dieser Materalien. Durch Verwendung von Metallen im erfindungsgemäßen Verfahren wird es möglich, den elektrischen Widerstand der Metalloberfläche entsprechend der Leitfähigkeit der elektrisch leitfähigen Polymere anzupassen, was in einigen Fällen (z.B. Abschirmung hochfrequenter Wellen) von Vorteil ist.Non-conductors are suitable as materials, but also electrical conductors such as metals. Non-conductive are e.g. thermoplastics, such as polyols. fine, polystyrene, polyamides, polyethers, polyurethanes, polyether sulfones, polyimides or polyamideimides. Polytetrafluoroethylene, polyesters, polyether ketones, polysulfones and polyetherimides can also be coated by the process according to the invention. Inorganic materials such as e.g. Glass or other silicate materials in question. Other suitable inorganic materials are e.g. Clay, ceramic materials, titanium dioxide (rutile, anatase), titanates and single crystals of Seignette salt. The above-mentioned titanates and single crystals of Seignette salt have a pronounced anisotropy of certain properties. The coating with electrically conductive polymers makes it possible to e.g. to be used in electrical switches. The surface of these materials can be smooth or open-pored and both crystalline and amorphous materials can be used. Of the metallically conductive materials, steel, titanium, cobalt, chromium, vanadium, aluminum, copper or any alloys of these materials are also suitable. By using metals in the method according to the invention, it becomes possible to adapt the electrical resistance of the metal surface according to the conductivity of the electrically conductive polymers, which is advantageous in some cases (e.g. shielding of high-frequency waves).

Das erfindungsgemäße Verfahren eignet sich weiterhin zur Beschichtung von verleimten oder unverleimten Holzwerkstoffen, z.B. Spanplatten, Sägespänen und Holz selbst.The method according to the invention is also suitable for coating glued or unglued wood-based materials, e.g. Chipboard, sawdust and wood itself.

Die erfindungsgemäß verwendeten Monomeren werden ausgewählt aus der Klasse der 5-gliedrigen und 6-gliedrigen Heterocyclen, die Stickstoff oder Schwefel als Heteroatome enthalten. Vorzugsweise enthalten diese Verbindungen außerdem ein konjugiertes ir-Eiektronensystem.The monomers used according to the invention are selected from the class of 5-membered and 6-membered heterocycles which contain nitrogen or sulfur as heteroatoms. Preferably, these compounds also contain a conjugated ir electron system.

Beispiele dieser Verbindungen sind solche aus der Klasse der Pyrrole und der Thiophene. Von den Pyrrolen eignen sich z.B. das unsubstituierte Pyrrol selbst aber auch N-substituierte Pyrrole, wie N-Alkylpyrrole. Es können aber auch andere substituierte Pyrrole, wie 3,4-Dialkylpyrrole mit C,-C,-Alkylgruppen oder 3,4-Dichlorpyrrole Verwendung finden. Von den Verbindungen der Klasse der Thiophene eignet sich insbesondere das unsubstituierte Thiophen selbst sowie 2-oder 3-Alkylthiophene, z.B. 2,3-Diethylthiophen. Diese genannten 5-gliedrigen heterocyclischen Verbindungen können auch zusammen mit anderen copolymerisierbaren Verbindungen, wie z.B. Furanen, Thiazol, Oxazol oder Imidazol polymerisiert werden. Aus der Klasse der 6-gliedrigen Heterocyclen werden hier nur Anilin oder Benzidin erwähnt.Examples of these compounds are those from the class of pyrroles and thiophenes. Of the pyrroles, e.g. the unsubstituted pyrrole itself but also N-substituted pyrroles, such as N-alkylpyrroles. However, other substituted pyrroles, such as 3,4-dialkylpyrroles with C, -C, alkyl groups or 3,4-dichloropyrroles, can also be used. Of the compounds of the class of thiophenes, unsubstituted thiophene itself and 2-or 3-alkylthiophenes, e.g. 2,3-diethylthiophene. These 5-membered heterocyclic compounds mentioned can also be used together with other copolymerizable compounds, e.g. Furans, thiazole, oxazole or imidazole can be polymerized. From the class of 6-membered heterocycles only aniline or benzidine are mentioned here.

Als Oxidationsmittel verwendet man vorteilhaft Sauerstoff enthaltende Oxidationsmittel, die, bezogen auf 1 Mol der zu polymerisierenden Verbindung, in Mengen von 0,1 bis 2 Molen Verwendung finden können. Größere Mengen an Oxidationsmittel sind nicht erforderlich, da die Menge ausreicht, die gesamten Monomere in Polymere umzuwandeln.The oxidizing agent used is advantageously an oxygen-containing oxidizing agent which, based on 1 mole of the compound to be polymerized, can be used in amounts of 0.1 to 2 moles. Larger amounts of oxidizing agent are not necessary since the amount is sufficient to convert the entire monomers into polymers.

Von den Oxidationsmitteln haben sich insbesondere Peroxosäuren und deren Salze, wie die Peroxodischwefelsäure und deren Alkali-und Ammoniumsalze bewährt. Vorzugsweise werden auch Peroxoboräte, Perchlorate oder Peroxochromate wie Natriumperborat, Kaliumdichromat oder Eisenperchlorat und Kupferperchlorat verwendet. Außerdem sind Permanganate wie Kaliumpermanganat geeignet, wenn man diesem geringe Mengen Säure zusetzt. Auch Wasserstoffperoxid kann verwendet werden, wobei hier in der Regel die Anwesenheit von Leitsalzen sehr vorteilhaft ist. Auch PbO2 oder Oxidationsmittel auf der Basis von Mn - (III) können verwendet werden.Of the oxidizing agents, peroxo acids and their salts, such as peroxodisulfuric acid and their alkali and ammonium salts, have proven particularly useful. Peroxoborates, perchlorates or peroxochromates such as sodium perborate, potassium dichromate or iron perchlorate and copper perchlorate are also preferably used. Permanganates such as potassium permanganate are also suitable if small amounts of acid are added to them. Hydrogen peroxide can also be used, the presence of conductive salts generally being very advantageous here. PbO 2 or oxidizing agents based on Mn - (III) can also be used.

Man kann die Oxidationsmittel eventuell zusammen mit einem Leitsalz oder die Monomeren zusammen mit einem Leitsalz auf die Oberfläche des Materials aufbringen. Die Polymerisation der Monomeren kann also in Gegenwart von Leitsalzen erfolgen, die auch als Komplexierungsmittel oder Dotierungsmittel bezeichnet werden. Als Leitsalze haben sich z.B. KHSO., Na2SO4, HCOOH, LiClO4, HCIO., Net4ClO4, NBu<, CIO,, KAIFJ, NaAIF6, KBF,, K2ZrF6, K2NiF4, HO2(NO3)2, H2SO4, FeCl3, NOPF., KAsF. oder NaPF. bewährt. Die Konzentration der Leitsalze ist vorteilhaft so bemessen, daß auf 3 mol des eingesetzten Monomeren oder der Gemische der Monomeren mindestens 1 mol der oben aufgeführten Leitsalze verwendet werden; werden beispielsweise FeCl3, oder FeClO4 verwendet, so wirken solche Verbindungen gleichermaßen als Leitsalze und als Oxidationsmittel. Sulfonsäuren des Pyrrols oder des Thiophens können sowohl als Monomere als auch als Leitsalze verwendet werden.The oxidizing agents can possibly be applied to the surface of the material together with a conducting salt or the monomers together with a conducting salt. The polymerization of the monomers can therefore take place in the presence of conductive salts, which are also referred to as complexing agents or doping agents. Examples of conductive salts include KHSO., Na 2 SO 4 , HCOOH, LiClO 4 , HCIO., Net 4 ClO 4 , NBu < , CIO ,, KAIF J , NaAIF 6 , KBF ,, K 2 ZrF 6 , K 2 NiF 4 , HO 2 (NO 3 ) 2 , H 2 SO 4 , FeCl 3 , NOPF., KAsF. or NaPF. proven. The concentration of the conductive salts is advantageously such that at least 1 mol of the conductive salts listed above are used per 3 mol of the monomers used or of the mixtures of the monomers; if, for example, FeCl 3 or FeClO 4 is used, such compounds act equally as conductive salts and as oxidizing agents. Sulphonic acids of pyrrole or thiophene can be used both as monomers and as conducting salts.

Gemäß einer bevorzugten Ausführungsform bringt man zunächst auf die Oberfläche des Materials ein Oxidationsmittel auf. Dieses erfolgt zweckmäßig in Lösung, wobei sich Wasser als Lösungsmittel gegebenenfalls in Abmischung mit organischen, mit Wasser mischbaren Lösungsmitteln bewährt hat. Es können aber auch organische Lösungsmittel, wie Dimethylsulfoxid, Methanol, Acetonitril, Ethylencarbonat, Propylencarbonat, Dioxan oder Tetrahydrofuran verwendet werden. Man arbeitet zweckmäßigerweise so, daß die Lösungen 0,1 bis 50 Gew.%, vorzugsweise 1 bis 20 Gew.% des Oxidationsmittels enthalten. Die Menge des zuzusetzenden Oxidationsmittels beträgt vorteilhaft von 0,1 bis 2 mol pro Mol der zu polymerisierenden Verbindung. Das Aufbringen der Monomeren kann aus der Gasphase oder aus einer Lösung erfolgen. Beide Möglichkeiten werden später näher erläutert.According to a preferred embodiment, an oxidizing agent is first applied to the surface of the material. This is expediently carried out in solution, water having proven useful as a solvent, if appropriate in a mixture with organic, water-miscible solvents. However, organic solvents such as dimethyl sulfoxide, methanol, acetonitrile, ethylene carbonate, propylene carbonate, dioxane or tetrahydrofuran can also be used. It is advantageous to work in such a way that the solutions contain 0.1 to 50% by weight, preferably 1 to 20% by weight, of the oxidizing agent. The amount of the oxidizing agent to be added is advantageously from 0.1 to 2 mol per mol of the compound to be polymerized. The monomers can be applied from the gas phase or from a solution. Both options are explained in more detail later.

Gemäß einer weiteren bevorzugten Ausführungsform mischt man zunächst eine Lösung des Monomeren mit einer Lösung des Oxidationsmittels. Als Lösungsmittel eignen sich die bei der vorstehenden Verfahrensvariante erwähnten Lösungsmittel. Zur besseren Durchmischung bzw. zur Homogenisierung kann die Verteilung der Reaktionspartner in einem Ultraschallfeld erfolgen. Gegebenenfalls können auch Detergentien, vorzugsweise in einer Menge von 0,01 bis 10 Gew.% bezogen auf die eingesetzten Monomere, zugesetzt werden.According to a further preferred embodiment, a solution of the monomer is first mixed with a solution of the oxidizing agent. The solvents mentioned in the above process variant are suitable as solvents. For better mixing or for homogenization, the reaction partners can be distributed in an ultrasound field. If necessary, detergents can also be added, preferably in an amount of 0.01 to 10% by weight, based on the monomers used.

Zum Aufbringen der Schicht des leitfähigen Polymeren auf die anderen Materialien werden eine Lösung des Monomeren und eine Lösung des Oxidationsmittels, gegebenenfalls mit dem Leitsalz, gemischt und unmittelbar danach wird die Mischung auf die Oberfläche des Werkstoffs aufgebracht. Das Mischen der Lösung erfolgt zweckmäßig in einer für derartige Zwecke geeigneten Mischvorrichtung, wie Mischvorrichtungen für Zweikomponentenlacke oder solchen Mischvorrichtungen die als Zweikomponenten-Sprühvorrichtungen dienen. Vorteilhaft werden die Lösungen in feinteiliger Form gemischt und die Mischung auf die Oberfläche der Materialien aufgebracht. Unmittelbar nach dem Mischen, d.h. vorzugsweise in einem Zeitraum von 10 bis 180 Sekunden nach dem Mischen soll die Mischung auf der Oberfläche des Materials verteilt sein. Die vorteilhaft für derartige Arbeitsweisen zu verwendenden Zweikomponenten-Sprühvorrichtungen sind bekannt und in verschiedenen Varianten in der Technik gebräuchlich.To apply the layer of the conductive polymer to the other materials, a solution of the monomer and a solution of the oxidizing agent, optionally with the conductive salt, are mixed and immediately afterwards the mixture is applied to the surface of the material. The mixing of the solution is expediently carried out in a mixing device suitable for such purposes, such as mixing devices for two-component paints or mixing devices which serve as two-component spraying devices. The solutions are advantageously mixed in finely divided form and the mixture is applied to the surface of the materials. Immediately after mixing, i.e. preferably within a period of 10 to 180 seconds after mixing, the mixture should be distributed on the surface of the material. The two-component spray devices to be used advantageously for such working methods are known and are used in various variants in technology.

Ein Vorteil dieser Ausführungsform besteht darin, daß hiermit die kontinuierliche Beschichtung von Materialien mit elektrisch leitfähigen Polymeren auf technisch sehr einfache Weise möglich ist, indem man die zu beschichtenden Materialien kontinuierlich an der verwendeten Spritz-bzw. Sprühvorrichtung vorbeiführt.An advantage of this embodiment is that it enables the continuous coating of materials with electrically conductive polymers in a technically very simple manner by continuously applying the materials to be coated to the spraying or. Spray device passes.

Besonders geeignet ist diese Variante zur kontinuierlichen Beschichtung von Polymerfilmen mit antistatischen Überzügen. Zu diesem Zweck werden das aufzubringende Monomere in einem Lösungsmittel oder in Dispersion (Lösung I) und eine Lösung des Oxidationsmittels, vorzugsweise zusammen mit einer Säure (Lösung II) in einer Mischvorrichtung gemischt und auf einen kontinuierlich an der Sprüh-bzw. Spritzeinrichtung vorbeigeführten Polymerfilm aufgebracht.This variant is particularly suitable for the continuous coating of polymer films with antistatic coatings. For this purpose, the monomer to be applied is mixed in a solvent or in dispersion (solution I) and a solution of the oxidizing agent, preferably together with an acid (solution II) in a mixing device and continuously applied to the spray or. Spray device applied polymer film applied.

Die Monomeren können in einem Lösungsmittel, wie z.B. Ethanol oder Gemische von Alkoholen mit Wasser, aber auch in Polymerlösungen, z.B. einer Lösung von Polyphenylsulfon in Dichlormethan eingesetzt werden. Die Konzentration der Monomeren, welche das elektrisch leitfähige Polymere liefern, beträgt zweckmäßigerweise 1 bis 25 Gew.%.The monomers can be in a solvent such as e.g. Ethanol or mixtures of alcohols with water, but also in polymer solutions, e.g. a solution of polyphenyl sulfone in dichloromethane. The concentration of the monomers which provide the electrically conductive polymer is advantageously 1 to 25% by weight.

Die Konzentration von Oxidationsmittel und, gegebenenfalls, der Säure in der Lösung, die mit der Monomerlösung gemischt wird, beträgt im allgemeinen ebenfalls nicht mehr als 25 Gew.% - (jeweils Oxidationsmittel und Säure).The concentration of oxidizing agent and, if appropriate, the acid in the solution which is mixed with the monomer solution is generally likewise not more than 25% by weight - (oxidizing agent and acid in each case).

Als Säuren, die der Lösung des Oxidationsmittel zugesetzt werden können, haben sich insbesondere organische Sulfonsäuren, z.B. Anthrachinonsulfonsäure und Phenylsulfonsäure sowie deren Derivate bewährt.In particular, organic sulfonic acids, e.g., as acids which can be added to the oxidizing agent solution. Anthraquinone sulfonic acid and phenyl sulfonic acid and their derivatives have been proven.

Aus den vorstehend geschilderten Verfahrensvarianten wird deutlich, daß im Falle der Verwendung eines Leitsalzes dieses der Lösung des Monomeren oder der Lösung des Oxidationsmittels oder der Mischung dieser beiden Lösungen zugesetzt werden kann.It is clear from the process variants described above that if a conductive salt is used, this can be added to the solution of the monomer or the solution of the oxidizing agent or the mixture of these two solutions.

Eine weitere Verfahrensvariante besteht darin, zunächst die Monomeren auf die Oberfläche der Materialien aufzubringen und anschließend das Oxidationsmittel.A further process variant consists in first applying the monomers to the surface of the materials and then the oxidizing agent.

In diesem Fall kann das zu beschichtende Material in einem Lösungsmittel, z.B. in Ethanol, Aceton oder Wasser, vorgelegt und mit den Monomeren getränkt werden. Durch Zugabe des Oxidatronsmitteis wird das Monomere anschließend in Polymere überführt.In this case the material to be coated can be in a solvent, e.g. in ethanol, acetone or water, and be soaked with the monomers. The monomer is then converted into polymers by adding the oxidatron.

Als Oxidationsmittel eignen sich die bereits für diesen Zweck vorstehend beschriebenen Verbindungen.The compounds already described above for this purpose are suitable as oxidizing agents.

Das Material kann vor der Aufbringung der Monomeren gegebenenfalls einer Behandlung, z.B. mit Säure, unterworfen werden, um die Haftung der Monomeren am Material zu erhöhen.The material may optionally be subjected to a treatment, e.g. with acid, to increase the adhesion of the monomers to the material.

Bei der Beschichtung von Holz und Holzmaterialien ist es häufig vorteilhaft, wenn auch nicht unbedingt erforderlich, den Werkstoff zunächst mit einer Lösung der Monomeren zu tränken, anschließend eine Behandlung mit organischen oder anorganischen Säuren durchzuführen und - schließlich das Material mit dem Oxidationsmittel zu behandeln. Die Säurebehandlung ist vorteilhaft, aber nicht unbedingt erforderlich. Nur beispielhaft seien hier als geeignete Säuren Essigsäure, Salzsäure, Perchlorsäure und organische Sulfonsäuren genannt.When coating wood and wood materials, it is often advantageous, if not absolutely necessary, to first soak the material with a solution of the monomers, then to carry out a treatment with organic or inorganic acids and - finally to treat the material with the oxidizing agent. Acid treatment is beneficial but not essential. Acetic acid, hydrochloric acid, perchloric acid and organic sulfonic acids are mentioned as examples of suitable acids.

Bei den Verfahrensvarianten, in denen Oxidationsmittel und/oder Leitsalz und Monomere in zeitlichem Abstand voneinander auf das Material aufgebracht werden, d.h. zunächst das Oxidationsmittel und anschließend die Monomeren oder zunächst die Monomeren und anschließend das Oxidationsmittel, ist es grundsätzlich möglich, die Monomeren aus der Gasphase oder aus einer Lösung aufzubringen. Häufig hat sich die Aufbringung aus der Gasphase als vorteilhaft erwiesen.In the case of the process variants in which oxidizing agents and / or conductive salt and monomers are applied to the material at intervals of one another, i.e. first the oxidizing agent and then the monomers or first the monomers and then the oxidizing agent, it is in principle possible to apply the monomers from the gas phase or from a solution. Application from the gas phase has often proven to be advantageous.

Vorteilhaft erfolgt die Aufbringung aus der Gasphase derart, daß man die zu beschichtenden Materialien (behandelt oder unbehandelt; vor oder nach Aufbringung von Oxidationsmittel und/oder Leitsalz) in ein Gefäß überführt, dieses evakuiert und anschließend das Material mit Monomerdämpfen behandelt. In jedem Fall ist es beim Aufbringen der Monomeren aus der Gasphase von Vorteil, eventuell noch von der Behandlung des Materials vorhandene Lösungsmittel vollständig zu entfernen.The application from the gas phase is advantageously carried out by transferring the materials to be coated (treated or untreated; before or after applying the oxidizing agent and / or conductive salt) into a vessel, evacuating the vessel and then treating the material with monomer vapors. In any case, when applying the monomers from the gas phase, it is advantageous to completely remove any solvents that may still be present in the treatment of the material.

Als Lösungsmittel für die Variante der Aufbringung der Monomeren aus einer Lösung haben sich vor allem wäßrige und alkoholische Lösungsmittel, Ether, Tetrahydrofuran und Aceton bewährt, um nur einige zu nennen.In particular, aqueous and alcoholic solvents, ethers, tetrahydrofuran and acetone have proven themselves as solvents for the variant of applying the monomers from a solution, to name just a few.

Die Dicke der auf den Materialien aufgebrachten Schichten aus elektrisch leitfähigen Polymeren ist in weiten Grenzen variabel, liegt im allgemeinen jedoch im Bereich von 0,1 bis 100 um. Für spezielle Anwendungen können die Schichten jedoch sowohl dicker als auch dünner sein.The thickness of the layers of electrically conductive polymers applied to the materials is variable within wide limits, but is generally in the range from 0.1 to 100 μm. For special applications, however, the layers can be either thicker or thinner.

Die Polymerisation der Monomeren erfolgt in einem Temperaturbereich von 0 bis 500°C, vorzugsweise zwischen 20 und 250°C.The monomers are polymerized in a temperature range from 0 to 500.degree. C., preferably between 20 and 250.degree.

Der Druck, bei dem die Polymerisation durchgeführt wird, ist an sich nicht kritisch. Zweckmäßigerweise arbeitet man bei einem Druck im Bereich von 10 kPa bis 100 MPa.The pressure at which the polymerization is carried out is not critical per se. It is expedient to work at a pressure in the range from 10 kPa to 100 MPa.

Die elektrische Leitfähigkeit der aufgebrachten Polymeren liegt im allgemeinen im Bereich von 10-7 bis 10 + Scm-', insbesondere im Bereich von 10-3 bis 10 Scm-'.The electrical conductivity of the applied polymers is generally in the range from 10 7 to 10 + Scm- ', in particular in the range from 1 0 3 to 10 Scm-'.

Man kann nach dem erfindungsgemäßen Verfahren die Schicht des leitfähigen Polymeren nur auf bestimmte Stellen des Materials aufbringen, kann also Muster, Bilder oder Schriftzeichen bzw. Schaltanordnungen auf den Werkstoff aufbringen. Genauso ist es möglich, den gesamten Werkstoff nach dem Verfahren mit einer leitfähigen polymeren Schicht zu versehen. Mitunter ist es angebracht, diesen Vorgang mehrfach zu wiederholen, wobei unterschiedliche leitfähige Polymere übereinander gelagert werden können. Wie bereits erwähnt, haftet die Schicht des leitfähigen Polymeren fest auf der Schicht des Materials. Eine Verbesserung der Haftfestigkeit der elektrisch leitfähigen Schicht auf den Materialien wird in vielen Fällen durch Tempern bei 80 bis 150°C - (natürlich in Abhängigkeit von der Erweichungstem- . peratur des zu beschichtenden Materials) erreicht.According to the method according to the invention, the layer of the conductive polymer can only be applied to certain points on the material, ie patterns, pictures or characters or switching arrangements can be applied to the material. It is also possible to provide the entire material with a conductive polymer layer after the process. It is sometimes appropriate to repeat this process several times, whereby different conductive polymers can be stacked on top of each other. As already mentioned, the layer of the conductive polymer adheres firmly to the layer of the material. An improvement in the adhesive strength of the electrically conductive layer on the materials is achieved in many cases by tempering at 80 to 150 ° C. (of course depending on the softening temperature of the material to be coated).

Nach dem erfindungsgemäßen Verfahren können beispielsweise antistatisch ausgerüstete Folien oder Folien für Verpackungen hergestellt werden, die zur Verpackung von Substanzen, die elekrisch abgeschirmt sein müssen. Auch lassen sich nach dem Verfahren der Erfindung Druckschalter sowie Schaltungen zur Informationsfixierung herstellen. Nach dem Verfahren hergestellte Verbundstoffe lassen sich für photovoltaische Elemente verwenden.The process according to the invention can be used, for example, to produce antistatic films or films for packaging which are used for packaging substances which have to be electrically shielded. Pressure switches and circuits for fixing information can also be produced by the method of the invention. Composites made by the process can be used for photovoltaic elements.

Weiterhin sind die nach dem erfindungsgemäßen Verfahren erhaltenen Materialien auch als Leiterbahnen und als Elektrodenmaterial geeignet. Bei der Verwendung als Leiterbahnen kann eine anschließende Modifizierung durch Laser oder eine andere energiereiche Strahlung erfolgen. Als Beispiel für die Anwendung als Elektrodenmaterial sei die Abscheidung von metallischem Kupfer erwähnt.Furthermore, the materials obtained by the process according to the invention are also suitable as conductor tracks and as electrode material. When used as conductor tracks, a subsequent modification by laser or other high-energy radiation can take place. The deposition of metallic copper may be mentioned as an example of the use as an electrode material.

Anorganische Materialien, die nach dem erfindungsgemäßen Verfahren beschichtet wurden, eignen sich z.B. als Dielektrika, zur Herstellung von Elektroden und zur Abschirmung elektromagnetischer Wellen sowie als Sensoren.Inorganic materials which have been coated by the process according to the invention are suitable, for example as dielectrics, for the production of electrodes and for shielding electromagnetic waves, and as sensors.

Beispiel 1example 1

Die Oberfläche eines Polyesterfilms (42 µ. dick) wurde mit einer 10 gew.%igen ethanolischen Lösung von Eisenperchlorat bestrichen. Man ließ das Lösungsmittel abdampfen und setzte den so behandelten Film bei einer Temperatur von 150°C 30 Sekunden einer Stickstoffatmosphäre aus, die 10 Vol.% Pyrroldampf enthielt. Innerhalb weniger Sekunden bildete sich an der Filmoberfläche eine - schwarze Schicht aus. Dieser unlösliche Polypyrrolüberzug hatte eine spezifische Leitfähigkeit von 10-' S/cm.The surface of a polyester film (42 .mu.m thick) was coated with a 10% by weight ethanolic solution of iron perchlorate. The solvent was allowed to evaporate and the film thus treated was exposed to a nitrogen atmosphere containing 10% by volume of pyrrole vapor at a temperature of 150 ° C. for 30 seconds. Within a few seconds a black layer formed on the film surface. This insoluble polypyrrole coating had a specific conductivity of 10- 'S / cm.

Beispiel 2Example 2

Es wurde wie in Beispiel 1 gearbeitet, jedoch als Filmmaterial Polyethersulfon verwendet. Die spezifische Leitfähigkeit des ausgebildeten Polypyrrolfilms betrug 10-' S/cm.The procedure was as in Example 1, but polyethersulfone was used as the film material. The specific conductivity of the formed polypyrrole film was 10- 'S / cm.

Beispiel 3Example 3

Es. wurde wie in Beispiel 1 gearbeitet, jedoch als Filmmaterial Polyetherketon verwendet. Die spezifische Leitfähigkeit des Polypyrrolfilms betrug 10-2 S/cm.It. the procedure was as in Example 1, but polyether ketone was used as film material. The specific conductivity of the polypyrrole film was 10 - / cm 2 S.

Beispiel 4Example 4

Ein Film aus Polyamid einer Dicke von 30 u wurde mit einer wäßrigen Lösung bestrichen, die 10 Gew.% Natriumperoxidisulfat und 5 Gew.% Benzolsulfonsäure enthielt. Das Wasser wurde abgedampft und der so behandelte Film einer Atmosphäre ausgesetzt, die wie in Beispiel 1 beschrieben aus Stickstoff und Pyrroldampf bestand. Es bildete sich ein unlöslicher festhaftender Film aus, der eine spezifische Leitfähigkeit von 0,2,10-' S/cm hatte.A film of polyamide 30 µm thick was coated with an aqueous solution containing 10% by weight sodium peroxydisulfate and 5% by weight benzenesulfonic acid. The water was evaporated and the film thus treated was exposed to an atmosphere consisting of nitrogen and pyrrole vapor as described in Example 1. An insoluble, adherent film was formed which had a specific conductivity of 0.2.10- 'S / cm.

Beispiel 5Example 5

Es wurde wie in Beispiel 1 beschrieben gearbeitet, jedoch wurde eine Lösung die 10 Gew.% Eisenperchlorat und 10 Gew.% Polyvinylalkohol enthält, aufgebracht und das Wasser abgedampft. Nach dem Einwirken der Pyrrol-Atmosphäre wurde ein Polypyrrolfilm erhalten, der fest auf der Polyestergrundlage haftete. Die spezifische Leitfähigkeit betrug 0,6,10-2 S/cm.The procedure was as described in Example 1, but a solution containing 10% by weight of iron perchlorate and 10% by weight of polyvinyl alcohol was applied and the water was evaporated off. After exposure to the pyrrole atmosphere, a polypyrrole film was obtained which adhered firmly to the polyester base. The specific conductivity was 0,6,10- 2 S / cm.

Beispiel 6Example 6

Eine Lösung von 10 Gew.% Pyrrol in Ethanol - (Lösung 1) und eine wäßrige Lösung von 10 Gew.% Na2S2O8 (Natriumperoxidisulfat) (Lösung II) wurden in einer Zweikomponentenspritzpistole gemischt und senkrecht gegen ein poliertes Holzstück gespült. Das Werkstück wurde 10 sek mit der Lösung I + II bespült und dann bei 60°C (1 h bei 10 Torr) getrocknet. Es entstand eine festhaftende Schicht eines schwarzen elektrisch leitfähigen Polymeren mit einer Leitfähigkeit von 8 S/cm.A solution of 10% by weight pyrrole in ethanol (solution 1) and an aqueous solution of 10% by weight Na 2 S 2 O 8 (sodium peroxydisulfate) (solution II) were mixed in a two-component spray gun and rinsed vertically against a polished piece of wood. The workpiece was rinsed with solution I + II for 10 seconds and then dried at 60 ° C. (1 hour at 10 torr). The result was a firmly adhering layer of a black, electrically conductive polymer with a conductivity of 8 S / cm.

Beispiel 7Example 7

Die Lösungen und II (wie in Beispiel 1) wurden gemischt und das Holzstück 20 sek in der Lösung gelagert. Die Leitfähigkeit des elektrisch leitfähigen Überzugs betrug nach dem Trocknen 5 S/cm.The solutions and II (as in Example 1) were mixed and the piece of wood was stored in the solution for 20 seconds. The conductivity of the electrically conductive coating was 5 S / cm after drying.

Beispiel 8Example 8

Die Lösungen I und 'II (wie in Beispiel 2) wurden gemischt und ein Gewebe (Leinen, 10 x 10 cm) wurde 20 sek in der Lösung gelagert. Die Leitfähigkeit betrug nach dem Trocknen 2,8 S/cm.Solutions I and 'II (as in Example 2) were mixed and a tissue (linen, 10 x 10 cm) was stored in the solution for 20 seconds. The conductivity after drying was 2.8 S / cm.

Beispiel 9Example 9

Man arbeitete wie in Beispiel 1, aber die Lösung 1 enthielt zusätzlich 3 Gew.% Benzolsulfonsäure. Nach dem Verfahren wie in Beispiel 1 wurde eine elektrisch leitfähige Schicht mit einer Leitfähigkeit von 7 S/cm erhalten.The procedure was as in Example 1, but solution 1 additionally contained 3% by weight of benzenesulfonic acid. Following the procedure as in Example 1, an electrically conductive layer with a conductivity of 7 S / cm was obtained.

Claims (6)

1. Verfahren zum Aufbringen von Schichten aus elektrisch leitfähigen Polymeren auf andere Materialien, dadurch gekennzeichnet, daß man Monomere aus der Gruppe der 5-und 6-gliedrigen Heterocyclen, die Stickstoff oder Schwefel als Heteroatome enthalten, auf das Material aufbringt und mit einem Oxidationsmittel polymerisiert.1. A process for applying layers of electrically conductive polymers to other materials, characterized in that monomers from the group of 5- and 6-membered heterocycles containing nitrogen or sulfur as heteroatoms are applied to the material and polymerized with an oxidizing agent . 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man eine Lösung des Monomeren und eine Lösung eines Oxidationsmittels mischt und die Mischung unmittelbar danach auf die Oberfläche des Materials aufbringt.2. The method according to claim 1, characterized in that a solution of the monomer and a solution of an oxidizing agent is mixed and the mixture is applied immediately afterwards to the surface of the material. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man auf die Oberfläche des Materials zunächst ein Oxidationsmittel und anschließend die Monomeren aufbringt.3. The method according to claim 1, characterized in that first an oxidizing agent and then the monomers are applied to the surface of the material. 4. Verfahren nach den Ansprüchen 1 bis 3, dadurch oekennzeichnet, daß man zusammen mit dem Oxidationsmittel und/oder den Monomeren ein Leitsalz auf die Oberfläche des Materials aufbringt.4. Process according to claims 1 to 3, characterized in that a conductive salt is applied to the surface of the material together with the oxidizing agent and / or the monomers. 5. Verfahren nach den Ansprüchen 1, 3 und 4, dadurch gekennzeichnet, daß man die Monomeren aus der Gasphase auf das Material aufbringt.5. Process according to claims 1, 3 and 4, characterized in that the monomers are applied to the material from the gas phase. 6. Verfahren nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß man als Monomere Thiophen, Pyrrol oder Anilin verwendet.6. Process according to claims 1 to 5, characterized in that thiophene, pyrrole or aniline are used as monomers.
EP86107994A 1985-06-12 1986-06-11 Use of polypyrrole to deposit metallic copper onto non-electroconductive materials Expired - Lifetime EP0206133B1 (en)

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DE3520980 1985-06-12
DE19853520980 DE3520980A1 (en) 1985-06-12 1985-06-12 Method for applying a layer of electrically conductive polymers to other materials
DE3535709 1985-10-05
DE19853535709 DE3535709A1 (en) 1985-10-05 1985-10-05 Process for applying a layer of electrically conductive polymers to other materials

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EP0206133A1 true EP0206133A1 (en) 1986-12-30
EP0206133B1 EP0206133B1 (en) 1991-07-31

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EP86107994A Expired - Lifetime EP0206133B1 (en) 1985-06-12 1986-06-11 Use of polypyrrole to deposit metallic copper onto non-electroconductive materials

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Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0219063A2 (en) * 1985-10-09 1987-04-22 Sanyo Electric Co., Ltd Process of manufacturing an electrically conductive material and a secondary battery using the electrically conductive material
EP0259813A2 (en) * 1986-09-10 1988-03-16 BASF Aktiengesellschaft Process for making a composite of an electrically conducting polymer and a ceramic material
EP0295676A2 (en) * 1987-06-19 1988-12-21 BASF Aktiengesellschaft Polymers obtained by oxidative polymerisation
EP0302590A2 (en) * 1987-08-03 1989-02-08 Milliken Research Corporation Method for making electrically conductive materials
EP0307683A2 (en) * 1987-09-05 1989-03-22 Bayer Ag Process for the antistatic treatment of hot melt adhesive layers
WO1989008375A1 (en) * 1988-03-03 1989-09-08 Blasberg-Oberflächentechnik Gmbh New through-hole plated printed circuit board and process for manufacturing same
DE3806884C1 (en) * 1988-03-03 1989-09-21 Blasberg-Oberflaechentechnik Gmbh, 5650 Solingen, De Through-plated contact printed circuit and method for fabricating it
EP0349105A1 (en) * 1988-06-27 1990-01-03 Milliken Research Corporation Method for making electrically conductive textile materials
EP0355518A2 (en) * 1988-08-03 1990-02-28 E.I. Du Pont De Nemours And Company Electrically conductiv articles
US4959430A (en) * 1988-04-22 1990-09-25 Bayer Aktiengesellschaft Polythiophenes, process for their preparation and their use
EP0411793A2 (en) * 1989-08-04 1991-02-06 British Aerospace Public Limited Company Preparation of conductive films and their use as gas sensors
EP0417750A2 (en) * 1989-09-14 1991-03-20 ATOTECH Deutschland GmbH Process for direct metallization of circuit boards
WO1991003920A2 (en) * 1989-08-31 1991-03-21 Blasberg-Oberflächentechnik Gmbh Plated-through printed circuit board with resist and process for producing it
DE3939676A1 (en) * 1989-11-28 1991-05-29 Schering Ag METALIZATION OF NON-CONDUCTORS
US5045357A (en) * 1987-12-09 1991-09-03 Mitsubishi Rayon Company, Ltd. Process for preparing a membranous gas separator
DE4023619A1 (en) * 1990-07-25 1991-09-19 Daimler Benz Ag Metallising electrically insulating substrate surface - by first impregnating with oxidant and gas phase deposition of conductive polymer, esp. used for fibre material
EP0456211A2 (en) * 1990-05-10 1991-11-13 Tomoegawa Paper Co. Ltd. Process for producing a composite comprising paper and electroconducting polymers
EP0457180A2 (en) * 1990-05-09 1991-11-21 LeaRonal (UK) plc Process for metallising a through-hole board
DE4211152C1 (en) * 1992-03-31 1993-11-25 Schering Ag Process for metallization of non-conductors and application of the process
AU644602B2 (en) * 1989-08-31 1993-12-16 Blasberg-Oberflachentechnik Gmbh Plated-through printed circuit board with resist and process for producing it
US5336374A (en) * 1990-05-10 1994-08-09 Tomoegawa Paper Co., Ltd. Composite comprising paper and electro-conducting polymers and its production process
DE4412463A1 (en) * 1994-04-08 1995-10-12 Atotech Deutschland Gmbh Palladium colloid solution and its use
EP0725454A1 (en) 1995-02-03 1996-08-07 Hoechst Trevira GmbH & Co. KG Active mass support and electrode for primary and secondary galvanic elements
DE19615201A1 (en) * 1996-04-18 1997-10-23 Univ Dresden Tech Metallising metal surfaces which are difficult to plate
US6174416B1 (en) 1996-10-09 2001-01-16 Robert Bosch Gmbh Micromechanical component production method
US6509169B2 (en) 2000-07-14 2003-01-21 University Of West England, Bristol Detection of Helicobacter pylori
EP1897974A1 (en) * 2006-09-07 2008-03-12 Enthone Inc. Deposition of conductive polymer and metallization of non-conductive substrates
DE19919261B4 (en) * 1999-04-28 2008-11-06 Plieth, Waldfried, Prof. Dr. Process for the production of ultra-thin compact, adherent and electrically conductive polymer layers on surfaces of oxidic particles, particles produced therewith and their use
CN101542021B (en) * 2006-09-07 2011-11-16 恩索恩公司 Deposition of conductive polymer and metallization of non-conductive substrates
US8366901B2 (en) 2006-09-07 2013-02-05 Enthone Inc. Deposition of conductive polymer and metallization of non-conductive substrates
DE102014001816A1 (en) 2014-02-13 2015-08-13 Jenabatteries GmbH Redox flow cell for storing electrical energy and its use
DE102015010083A1 (en) 2015-08-07 2017-02-09 Friedrich-Schiller-Universität Jena Redox flow cell for storing electrical energy and its use
DE102015014828A1 (en) 2015-11-18 2017-05-18 Friedrich-Schiller-Universität Jena Hybrid flow cell for storing electrical energy and its use

Citations (4)

* Cited by examiner, † Cited by third party
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EP0053669A1 (en) * 1980-11-24 1982-06-16 BASF Aktiengesellschaft Method of making electroconductive copolymers and use thereof in the electrotechnology, and in imparting antistatic properties to plastics
DE3200073A1 (en) * 1981-01-10 1982-08-12 Basf Ag, 6700 Ludwigshafen Process for the preparation of electroconductive polymers, and the use thereof in electrical engineering and for antistatic finishing of plastics
DE3321281A1 (en) * 1982-06-22 1983-12-22 ASEA AB, 72183 Västerås METHOD FOR INCREASING THE ELECTRICAL CONDUCTIVITY OF IMPREGNABLE MATERIALS
EP0152632A2 (en) * 1983-12-30 1985-08-28 Nitto Denko Corporation Electroconductive porous film and process for producing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0053669A1 (en) * 1980-11-24 1982-06-16 BASF Aktiengesellschaft Method of making electroconductive copolymers and use thereof in the electrotechnology, and in imparting antistatic properties to plastics
DE3200073A1 (en) * 1981-01-10 1982-08-12 Basf Ag, 6700 Ludwigshafen Process for the preparation of electroconductive polymers, and the use thereof in electrical engineering and for antistatic finishing of plastics
DE3321281A1 (en) * 1982-06-22 1983-12-22 ASEA AB, 72183 Västerås METHOD FOR INCREASING THE ELECTRICAL CONDUCTIVITY OF IMPREGNABLE MATERIALS
EP0152632A2 (en) * 1983-12-30 1985-08-28 Nitto Denko Corporation Electroconductive porous film and process for producing same

Cited By (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0219063A3 (en) * 1985-10-09 1989-03-22 Sanyo Electric Co., Ltd. Electrically conductive material and secondary battery using the electrically conductive material
EP0219063A2 (en) * 1985-10-09 1987-04-22 Sanyo Electric Co., Ltd Process of manufacturing an electrically conductive material and a secondary battery using the electrically conductive material
EP0259813A2 (en) * 1986-09-10 1988-03-16 BASF Aktiengesellschaft Process for making a composite of an electrically conducting polymer and a ceramic material
EP0259813A3 (en) * 1986-09-10 1989-10-25 BASF Aktiengesellschaft Process for making a composite of an electrically conducting polymer and a ceramic material
EP0295676A3 (en) * 1987-06-19 1990-05-16 BASF Aktiengesellschaft Polymers obtained by oxidative polymerisation
EP0295676A2 (en) * 1987-06-19 1988-12-21 BASF Aktiengesellschaft Polymers obtained by oxidative polymerisation
EP0302590A2 (en) * 1987-08-03 1989-02-08 Milliken Research Corporation Method for making electrically conductive materials
EP0302590A3 (en) * 1987-08-03 1989-12-13 Milliken Research Corporation Electrically conductive textile materials and method for making same
EP0307683A2 (en) * 1987-09-05 1989-03-22 Bayer Ag Process for the antistatic treatment of hot melt adhesive layers
EP0307683A3 (en) * 1987-09-05 1991-01-02 Bayer Ag Process for the antistatic treatment of hot melt adhesive layers
US5045357A (en) * 1987-12-09 1991-09-03 Mitsubishi Rayon Company, Ltd. Process for preparing a membranous gas separator
US5154740A (en) * 1987-12-09 1992-10-13 Mitsubishi Rayon Co., Ltd. Membranous gas separator
DE3806884C1 (en) * 1988-03-03 1989-09-21 Blasberg-Oberflaechentechnik Gmbh, 5650 Solingen, De Through-plated contact printed circuit and method for fabricating it
WO1989008375A1 (en) * 1988-03-03 1989-09-08 Blasberg-Oberflächentechnik Gmbh New through-hole plated printed circuit board and process for manufacturing same
US4959430A (en) * 1988-04-22 1990-09-25 Bayer Aktiengesellschaft Polythiophenes, process for their preparation and their use
US4987042A (en) * 1988-04-22 1991-01-22 Bayer Aktiengesellschaft Polythiophenes, process for their preparation and their use
EP0349105A1 (en) * 1988-06-27 1990-01-03 Milliken Research Corporation Method for making electrically conductive textile materials
EP0355518A3 (en) * 1988-08-03 1990-12-19 E.I. Du Pont De Nemours And Company Electrically conductiv articles
EP0355518A2 (en) * 1988-08-03 1990-02-28 E.I. Du Pont De Nemours And Company Electrically conductiv articles
EP0411793A3 (en) * 1989-08-04 1991-07-24 British Aerospace Plc Preparation of conductive films and their use as gas sensors
EP0411793A2 (en) * 1989-08-04 1991-02-06 British Aerospace Public Limited Company Preparation of conductive films and their use as gas sensors
GB2234515A (en) * 1989-08-04 1991-02-06 British Aerospace Preparation of polypyrrole conductive films and their use as gas sensors
GB2234515B (en) * 1989-08-04 1992-09-30 British Aerospace Preparation of conductive films and their use as gas sensors
WO1991003920A3 (en) * 1989-08-31 1991-04-18 Blasberg Oberflaechentech Plated-through printed circuit board with resist and process for producing it
US5373629A (en) * 1989-08-31 1994-12-20 Blasberg-Oberflachentechnik Gmbh Through-hole plate printed circuit board with resist and process for manufacturing same
WO1991003920A2 (en) * 1989-08-31 1991-03-21 Blasberg-Oberflächentechnik Gmbh Plated-through printed circuit board with resist and process for producing it
AU644602B2 (en) * 1989-08-31 1993-12-16 Blasberg-Oberflachentechnik Gmbh Plated-through printed circuit board with resist and process for producing it
EP0417750A3 (en) * 1989-09-14 1991-10-30 Schering Aktiengesellschaft Berlin Und Bergkamen Process for direct metallization of circuit boards
EP0417750A2 (en) * 1989-09-14 1991-03-20 ATOTECH Deutschland GmbH Process for direct metallization of circuit boards
DE3939676A1 (en) * 1989-11-28 1991-05-29 Schering Ag METALIZATION OF NON-CONDUCTORS
EP0457180A2 (en) * 1990-05-09 1991-11-21 LeaRonal (UK) plc Process for metallising a through-hole board
EP0457180A3 (en) * 1990-05-09 1991-11-27 LeaRonal (UK) plc Process for metallising a through-hole board
EP0456211A2 (en) * 1990-05-10 1991-11-13 Tomoegawa Paper Co. Ltd. Process for producing a composite comprising paper and electroconducting polymers
EP0456211A3 (en) * 1990-05-10 1992-02-19 Tomoegawa Paper Co. Ltd. Composite comprising paper and electroconducting polymers and its production process
US5336374A (en) * 1990-05-10 1994-08-09 Tomoegawa Paper Co., Ltd. Composite comprising paper and electro-conducting polymers and its production process
US5421959A (en) * 1990-05-10 1995-06-06 Tomegawa Paper Co., Ltd. Composite comprising paper and electro-conducting polymers and its production process
DE4023619A1 (en) * 1990-07-25 1991-09-19 Daimler Benz Ag Metallising electrically insulating substrate surface - by first impregnating with oxidant and gas phase deposition of conductive polymer, esp. used for fibre material
DE4211152C1 (en) * 1992-03-31 1993-11-25 Schering Ag Process for metallization of non-conductors and application of the process
DE4412463A1 (en) * 1994-04-08 1995-10-12 Atotech Deutschland Gmbh Palladium colloid solution and its use
DE4412463C3 (en) * 1994-04-08 2000-02-10 Atotech Deutschland Gmbh Process for the preparation of a palladium colloid solution and its use
EP0725454A1 (en) 1995-02-03 1996-08-07 Hoechst Trevira GmbH & Co. KG Active mass support and electrode for primary and secondary galvanic elements
DE19615201A1 (en) * 1996-04-18 1997-10-23 Univ Dresden Tech Metallising metal surfaces which are difficult to plate
US6174416B1 (en) 1996-10-09 2001-01-16 Robert Bosch Gmbh Micromechanical component production method
DE19919261B4 (en) * 1999-04-28 2008-11-06 Plieth, Waldfried, Prof. Dr. Process for the production of ultra-thin compact, adherent and electrically conductive polymer layers on surfaces of oxidic particles, particles produced therewith and their use
US6509169B2 (en) 2000-07-14 2003-01-21 University Of West England, Bristol Detection of Helicobacter pylori
EP1897974A1 (en) * 2006-09-07 2008-03-12 Enthone Inc. Deposition of conductive polymer and metallization of non-conductive substrates
CN101542021B (en) * 2006-09-07 2011-11-16 恩索恩公司 Deposition of conductive polymer and metallization of non-conductive substrates
US8366901B2 (en) 2006-09-07 2013-02-05 Enthone Inc. Deposition of conductive polymer and metallization of non-conductive substrates
DE102014001816A1 (en) 2014-02-13 2015-08-13 Jenabatteries GmbH Redox flow cell for storing electrical energy and its use
WO2015120971A1 (en) 2014-02-13 2015-08-20 Jenabatteries GmbH Redox flow cell for storing electrical energy and use thereof
DE102015010083A1 (en) 2015-08-07 2017-02-09 Friedrich-Schiller-Universität Jena Redox flow cell for storing electrical energy and its use
US11515557B2 (en) 2015-08-07 2022-11-29 Jenabatteries GmbH Redox flow cell for storing electrical energy and use thereof
DE102015014828A1 (en) 2015-11-18 2017-05-18 Friedrich-Schiller-Universität Jena Hybrid flow cell for storing electrical energy and its use
US11283077B2 (en) 2015-11-18 2022-03-22 Jena Batteries, Gmbh Hybrid flow battery for storing electrical energy and use thereof

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DE3680592D1 (en) 1991-09-05

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